A switchable diode in a 2D semiconductor-molecular junction heterostructure is reported. MoS2 is exfoliated on top of a monolayer of azobenzene-substituted thiols on gold. Photoisomerization of the azobenzenes results in switching between a rectifier with rectifying ratios of 10(4) and a conductive state, as revealed by conducting atomic force microscopy.

On-surface chemistry for atomically precise sp(2) macromolecules requires top-down lithographic methods on insulating surfaces in order to pattern the long-range complex architectures needed by the semiconductor industry. Here, we fabricate sp(2)-carbon nanometer-thin films on insulators and under ultrahigh vacuum (UHV) conditions from photocoupled brominated precursors. We reveal that covalent coupling is initiated by C-Br bond cleavage through photon energies exceeding 4.4 eV, as monitored by laser desorption ionization (LDI) mass spectrometry (MS) and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) gives insight into the mechanisms of C-Br scission and C-C coupling processes. Further, unreacted material can be sublimed and the coupled sp(2)-carbon precursors can be graphitized by e-beam treatment at 500 °C, demonstrating promising applications in photolithography of graphene nanoarchitectures. Our results present UV-induced reactions on insulators for the formation of all sp(2)-carbon architectures, thereby converging top-down lithography and bottom-up on-surface chemistry into technology.

Reversible work function changes induced by photoisomerization of asymmetric azobenzene dithiol selfassembled monolayers on gold Appl. Phys. Lett. 93, 083109 (2008); 10.1063/1.2969468Monolayer alignment on azobenzene surfaces during UV light irradiation: Analysis of optical polarized absorption measurement results and theoretical treatment